CN1522201A

CN1522201A - Multilayer polymeric films

Info

Publication number: CN1522201A
Application number: CNA028134397A
Authority: CN
Inventors: D・H・麦克伦; D·H·麦克伦; 弗里恩德; J·E·弗里恩德
Original assignee: AMERIC DUONT TAKIN FILMS PARTNERS Inc
Current assignee: AMERIC DUONT TAKIN FILMS PARTNERS Inc; DuPont Teijin Films US LP
Priority date: 2001-05-02
Filing date: 2002-04-25
Publication date: 2004-08-18
Anticipated expiration: 2022-04-25
Also published as: DE60221013D1; EP1395426B1; AU2002249461A1; JP2004525005A; CN100349735C; WO2002087873A3; US7255928B2; JP4651911B2; KR20040015243A; GB0110799D0; WO2002087873A2; EP1395426A2; US20050058825A1; DE60221013T2

Abstract

The use of multilayer film structure comprising at least two unfilled layers of polymeric material substantially devoid of opacifying agent and at least two filled layers of polymeric material wherein said filled layers comprise at least 5 % by weight of opacifying agent for providing improved tear-resistance in an opaque polymeric film, particularly a polyester film.

Description

Multilayer polymer film

The present invention relates to opaque multilayer polymer film.

Opaque polymer film is well-known in the art and has various uses, comprise usually purposes as the substitute (film that for example is used for drawing, demonstration, label, card (comprising identity card, smart card and credit card) and imaging) of paper, as the purposes of printed panel medium, purposes in packing and the purposes in coil coating.Opaque film prepares by adding filler and pigment, particularly Chinese white in film forming polymer usually.

The manufacturing cost of thin polymer film is subjected to the influence of Several Factors, comprise additive amount and price, additive is introduced the complexity of the technology in the film and the efficient of manufacturing process.The manufacturing cost of opaque film is higher than the not manufacturing cost of filled with film certainly, because the cost of annexing ingredient.Therefore, although add the opacity that relatively large filler can correspondingly improve film, the conventional practice is to trade off or average out between the cost and the opacity that will reach in the manufacturing process of routine.

Except that the cost that improves, add filler and also have other shortcoming.Although add filler and be regulate film transmitance can make things convenient for means, its mechanical performance to film may have adverse effect.Especially, add the tear-resistant performance that filler may influence film unfriendly.During manufacturing process, in order to improve economy, efficient and productive rate, high resistance to tearing is favourable.For the general processing of film and the last use of film, high resistance to tearing also is favourable.

In the manufacturing process of routine, used bigger film thickness, so that compensation is by using the caused adverse effect to mechanical performance of filler.In order to introduce enough fillers,, also require bigger film thickness with respect to the transparent membrane that has on a small quantity or do not have filler to obtain necessary opacity.Thicker film requires to use relatively large film forming polymer, and this has improved manufacturing cost equally.Therefore, can keep necessary opacity and the film than minimal thickness with good resistance to tearing, be desirable for the market of Price Sensitive economically.

Tear-resistant film is well known in the art.EP-0592284 discloses tear-resistant plural layers, and it comprises the alternating layer of rigidity and toughness polymer material, and it can be used as the shockproof laminated material that is used for the glazing article.US-5759467 discloses the multi-layered polyester film, and it comprises the alternating layer of multiple terephthalic acid groups polyester and naphthalenedicarboxylic acid base polyester.This film has the hot strength of raising, and allegedly can be used for especially magnetizing mediums base material.

The preparation of plural layers can be carried out in every way.US-3647612 discloses the method that is used to prepare plural layers, it comprises: the logistics of two or more thermoplastics is provided, described two or more logistics are arranged in the single logistics with a plurality of usually parallel layers, by separating and, then described logistics being configured as thin sheet material or film again in conjunction with mechanically controlling logistics so that the number of plies of increase to be provided.Described layer is made up of resinous material, and it is transparent to visible light, and this multi-layer film structure has the outward appearance of iris.EP-0426636 also discloses multi-layer co-extruded optical reflection film, and it comprises a plurality of layers of parallel transparent thermoplastic resin's class material usually.

EP-0492894 discloses and has been used for by producing the method and apparatus that interface surface is produced plural layers at flowing material.This method may further comprise the steps: the first composite logistics is divided at least two branch's logistics, branch's logistics resets, along an expansion axisymmetrically, shrink axisymmetrically along another, with with this branch's logistics again in conjunction with forming the second composite logistics, it compares the discrete layer of the polymeric material that comprises greater number with the first composite logistics, wherein expansion and collapse step are being carried out in the logistics of single branch or carried out in the second composite logistics.

WO-98/06587 discloses the polyester film of the sandwich layer with opaque, preferred black, and this sandwich layer has and is higher than 2.0 optical density, and it is outer to have white on two surface, this polyester film be used to photograph sheet material or other imaging applications.

EP-A-0933199 discloses to have at least one and comprises the polyester layer that is higher than 5wt% pigment and at least one opaque plural layers of unpigmented polyester layer basically, wherein unpigmented layer with have pigment layer the ratio of respective thickness be at least 1.It is said that this film minimizes total pigment content, and high opacity and good mechanical performance (modulus, hot strength and the power under 3% percentage elongation, 5% percentage elongation, and elongation at break) are provided simultaneously.

General objects of the present invention is the balance between the film performance of influence and the efficient of improving thin film fabrication and hope.Therefore, an object of the present invention is to reduce production cost, but keep or improve the film performance of hope simultaneously.Another object of the present invention is to improve the performance of film and do not improve production cost.Especially, the purpose of this invention is to provide opaque film, its manufacturing is economical and it has improved resistance to tearing.Another object of the present invention is to reduce the thickness of opaque film, keeps necessary opacity and maintenance simultaneously simultaneously or improves resistance to tearing.Another object of the present invention provides the opacity that has raising for given thickness, keeps or improved the film of resistance to tearing simultaneously, has therefore improved manufacturing efficient.

According to the present invention, provide multi-layer substrate or structure to be used for providing the purposes of the resistance to tearing of raising at opaque highly-filled thin polymer film, described multi-layer substrate or structure comprise the layer of polymeric material of at least two unfilled essentially no opacifying agents and the layer of the polymeric material of at least two fillings, the opacifying agent that layer comprises at least 5% weight of wherein said filling.

According to another aspect of the present invention, opaque plural layers are provided, it comprises the layer of polyester material of at least two unfilled essentially no opacifying agents and the layer of the polymeric material of at least two fillings, the opacifying agent that layer comprises at least 5% weight of wherein said filling.

For for simplicity, term " unfilled layer " is used herein to the layer of the polymeric material that refers to essentially no opacifying agent (perhaps filler), and term " layer of filling " is used herein to the layer of polymeric material that finger comprises the opacifying agent of at least 5% weight.

At this, the filler of % weight unless otherwise mentioned, is meant with respect to the gross weight of film or with respect to the weight of the filler of the gross weight (being the weight that film forming or cambial polymeric material adds filler) of given layer.

For given opacity, with respect to the film that does not have described sandwich construction, plural layers described here can reduce the amount of filler in the film generally.Therefore, for given opacity, plural layers described here can reduce the amount of filler with respect to the single thin film of filling.Usually, for given packing density, different fillers produces different opacities.

The resistance to tearing that film described here has good opacity and unexpectedly improves.Described film can use less filler, keeps the opacity of conventional opaque film simultaneously, and its production is more economical.The unexpected benefit of resistance to tearing is meant:

(i), can produce thin film for given opacity and resistance to tearing; Perhaps

(ii) for given opacity and film thickness, the film that can the production resistance to tearing improves has the production efficiency of raising; Perhaps

(iii) for given thickness and resistance to tearing, the opacity of film can improve, promptly in the film amount of filler and therefore opacity can improve, and do not reduce the resistance to tearing of film or unfriendly influence make efficient.

In one embodiment, in whole film, the amount of filler that plural layers preferably comprise, based on the amount of filler in the single thin film with equal opacity, for less than about 90%, preferably less than about 80%, preferably less than about 70% with preferably less than about 60%.As mentioned above, this class film reduces film thickness for given opaqueness, and does not influence resistance to tearing unfriendly and make efficient.In this embodiment, in the plural layers weight of the total amount based thin film of filler preferably less than about 18%, preferably less than about 16%, preferably less than about 12%, preferably less than about 8% with preferably less than about 4%.As mentioned above, different fillers provide different opacities.If in this embodiment and described filler be barium sulfate, in the film weight of the total amount based thin film of filler be less than about 18%, preferably less than about 16% with preferably less than 12% weight.If described filler is for example titanium dioxide or polypropylene, the total amount of filler be less than about 16%, preferably less than 12%, preferably less than 8% with preferably less than 4%.

In selectable embodiment, in whole film, the amount of filler that plural layers comprise based on the amount of the filler in the single thin film with equal resistance to tearing, is at least 110%, preferably at least 120%, preferably at least 130% and preferably at least 140%.As mentioned above, this class film can improve opacity for given film thickness, and does not influence resistance to tearing unfriendly and make efficient.In this embodiment, in the plural layers weight of the total amount based thin film of filler can be higher than about 15%, preferably be higher than about 20%, preferably be higher than about 22% and preferably be higher than about 25% weight.For the barium sulfate filler, for example, in the film total amount of filler can be higher than 22% and preferred 25% or more than.

The level that opacifying agent exists in packed layer, the weight based on the polymeric material of packed layer is at least 5%, preferably at least 10% and more preferably at least 15%.Preferably, the amount of opacifying agent in the packed layer is based on the weight of the polymeric material of packed layer, for being not more than 30% and preferably be not more than 25%.

The tear resistance of film described here uses two parameter characterizations, i.e. " peak load " and " tearing toughness ".

Peak load is to measure the power that causes that film is torn to be needed, and promptly tears the yardstick of the load when beginning, and measures according to ASTM D1004-94A (Graves tear test).This parameter is called anti-initial tear fragility in ASTMD1004-94A, and represents with newton or kilogram.Peak load (being called anti-initial tear fragility in the Graves tear test) improves along with the raising of film thickness usually.Therefore,, importantly the film with similar thickness is tested, perhaps, determined the quantitative relationship between thickness and the peak load at first at the film type in the research for the purpose of justice contrast.In this research, the data declaration of having collected, peak load changes pro rata with thickness approx, and can use the Graves tear test to contrast the polyester film that thickness is in the filling in 50 to 125 mu m ranges reliably.Therefore, report after the measurement of this peak load is being standardized as the reference thickness of 80 μ m.Preferably, described film is to have at least 3.0kgf, preferred 3.5kgf at least and the more preferably peak load of 4.0kgf at least under the 80 μ m at film thickness.

Tear toughness and measure with the Graves area of film, described as EP-A-0592284.The Graves area carries out the mathematics integration by the stress to the film that carries out Graves tear test (ASTM D1004-94A) to the area below the curve in the strain figure and obtains, promptly during the Graves tear test, the film sample that is used for the Graves tear test of moulding is sandwiched between the relative clamp especially, clamp separates with constant speed, thereby tear stress is concentrated in little area.The load that stress is defined as writing down is divided by initial film cross-sectional area, and is opposite with the cut-out feature of sample.Strain be defined between initial gap (1) clamp of test period with respect to clamp huge from variation (Δ 1), i.e. strain is a Δ 1/1.

Therefore, tear the tolerance that toughness can think to cause the gross energy that film destruction needs, i.e. film endergonic ability before destroying.Should be appreciated that with having the less film of tearing toughness value and compare that having the film of tearing toughness value more greatly needs bigger gross energy to cause destruction.To tear toughness be on the machine direction of film according to test or carry out in the horizontal changing.

Preferably, the tear toughness of plural layers described here in one or two sizes of film equals 0.3kg/mm at least ², preferred 0.6kg/mm at least ²More preferably 0.9kg/mm at least ²

Preferred described opaque plural layers comprise at least 5 layers, preferably at least 6 layers and preferred 7 or more multi-layered.The sum in film middle level usually by the film thickness of hope and whether easily manufacturing determine.Usually, film has and is less than 100 layers.In one embodiment, film has and is less than 50 layers.The number of plies can be regulated according to the target thickness and the target opacity of film.For given film thickness, the number of plies will depend on for example thickness of individual layer and the particle size of filler.For example, for the thick film of 20 μ m, its filler and thickness in monolayer that comprises the average particle size of 1 μ m diameter is 0.5 μ m, and the number of plies should not surpass about 40.

Preferred film comprises packed layer and packed layer not alternately, promptly packed layer be arranged in two not between the packed layer and not packed layer be arranged between two packed layers.

In preferred embodiments, two of film outermost layers layer that is same type, be preferably packed layer.If skin is identical type, there is the layer of odd number in the preferred film, make in whole film each not packed layer and packed layer adjacency.

This film can have for example sandwich construction (BA) _n, (BA) _nB or (AB) _nA, wherein A represents not packed layer, B represents that packed layer and n are at least 2 integers, preferably at least 3 and preferably at least 4.Preferably, this film has structure (BA) _nB, preferably wherein n is at least 3 and preferably at least 4.

The thickness of each layer and the gross thickness of film can change in wide limit within the scope of the present invention.Practical film thickness is only limited by the desired process performance.The lower bound of useful actual range is meant, and is too weak at this film, be not easy to handle or do not have enough resistances to tearing, and useful high limit is meant, in this film undue rigidity that becomes, therefore is difficult to processing.

The gross thickness of plural layers described here is preferably about 5 to about 350 μ m, preferably approximately 5 to about 200 μ m.In one embodiment, film thickness is preferably about 5 to about 100 μ m, more preferably about 5 to about 50 μ m, more preferably about 5 to about 20 μ m and especially about 12 to about 20 μ m.In selectable embodiment, film thickness is about 50 to about 125 μ m.The thickness of individual layer also can change in wide region, should be appreciated that the thickness of each layer reduces when improving the number of plies under film thickness constant or that reduce.Single packed layer has the average thickness of about at least 0.1 μ m and in one embodiment usually, has the average thickness of about at least 0.5 μ m.Although the thickness of each layer can be identical, preferred packed layer is not than filling bed thickness, promptly packed layer and not the thickness ratio of packed layer greater than 1: 1.Packed layer is suitably about 99: 1 to about 0.05: 1, preferably approximately 50: 1 to about 0.05: 1 and preferably approximately 10: 1 to about 1: 1 with the thickness ratio of packed layer not.

Each of two class layers is not promptly filled and packed layer, the stretch modulus that has the stretch modulus of another kind of layer ± 25%, preferred ± 15%, more preferably ± 5% within the scope.In one embodiment, two class layers have substantially the same stretch modulus.The stretch modulus of the polymeric material of preferred each layer greater than 1380MPa, be preferably greater than 2000MPa, be preferably greater than 2070MPa, be preferably greater than 2760MPa and be preferably greater than 3000MPa.

The corresponding layer of plural layers can be formed by any filmogen, especially polyester, He Cheng linear polyester for example, it can prepare by one or more dicarboxylic acids or its low alkyl group (the highest 6 carbon atoms) diester and one or more glycol condensations, described dicarboxylic acids or its low alkyl group diester for example are terephthalic acid (TPA)s, M-phthalic acid, phthalic acid, 2,5-, 2,6-or 2, the 7-naphthalene dicarboxylic acids, butanedioic acid, decanedioic acid, adipic acid, azelaic acid, 4,4 '-diphenyl dicarboxylic acid, hexahydroterephthalic acid or 1,2-pair-to carboxyl phenoxy group ethane (randomly using monocarboxylic acid, for example neopentanoic acid), described glycol is aliphatic or alicyclic diol especially, ethylene glycol for example, 1, ammediol, 1, the 4-butanediol, neopentyl glycol and 1, the 4-cyclohexanedimethanol.Aliphatic diol is preferred.PETG or PEN are preferred polyester.PETG is especially preferred.

In the preferred embodiment of the invention, each class layer of plural layers comprises identical materials, preferred identical polyester.Preferably, the material that constitutes various layer is machinable and have similar melt viscosity under identical temperature, so that avoid damaging more low-melting material.Therefore, the time of staying and processing temperature must be regulated according to the properties of materials of each layer.Also preferred described layer comprises crystallization and/or semicrystalline polyester material.

The formation of plural layers can be undertaken by any technology known in the art.Yet, be easily, the moulding of laminated film is undertaken by coextrusion, both can by corresponding film forming layer by the independently nozzle of porous dies and after this will be still the layer associating of fusion the time co-extrusion come out to carry out, also can preferably come out to carry out by the single channel co-extrusion, after this wherein at first combination in the passage that leads to the die head manifold of the molten material flows of the material of corresponding film forming layer extrudes from die orifice under the laminar flow condition that does not have mixing together.

A kind of this class technology is disclosed in United States Patent (USP) 3,565,985 (Schrenk etc.).In making plural layers, can use by means of many-manifold die or wherein under laminar flow condition single layer contact and the melt coextrusion of the feed head method of integral multi-layered film be provided.More specifically, but the independent flow of material that is in each layer of flow regime is divided into the less tributary of predetermined number separately.Then, these less logistics merge in the mode of predetermined layer, but form a series of layer of these materials that are in flow regime.Each layer contacts closely with adjacent layer in this arrangement.This arrangement constitutes the lamination of high layer usually, and it is compressed then to reduce height.In branch manifold die head method, thin-film width keeps constant between the compression period of lamination, and thin-film width is expanded in feed head method.In both cases, all obtain thin wide film.Can also use layer times device (Layer multipliers), the film that wherein obtains is divided into many single subgrade films (subfilm), and this subgrade film is by stacked to increase the number of plies in last film mutually then.

In one embodiment, the preparation of plural layers is according to describing among the US-3051453 (publish and be Re.28,072) and carrying out in the program of Fig. 1 illustrated.This patent report a kind of method, wherein will comprise from the coextrusion melt-flow (BAB) of the layer of three separation of two kinds of polymer and cutting apart, be combined into the lamination of five different layers (BABAB) subsequently again.This program can repeat to comprise with production the single melt-flow of senior layer structure, and it can be extruded as for example film of molded article then.In fact, recent report shows, in the coextrusion melt process, in series introduce 7 layer multiplication units of as many as after, can produce the sandwich construction (Tech.Papers rolls up 42,1587 pages, 1996 for Nazarenko etc., SPE Inc.) of symmetry.

The film of describing in an embodiment prepares according to the program that US-3051453 describes hereinafter.The coextrusion melt that comprises three layers (BAB) is processed by two or three layers multiplication units.Then, the multilayer melt guiding that obtains is carried out curtain coating by slot die, quenching is a film then.

In further embodiment, the preparation of plural layers can use the layer multiplier on the combined-flow of the coextrusion polymer material layer that comprises separation to carry out, as in hereinafter and described in Fig. 2, wherein the z-axle is the flow direction of first combined-flow, the x-axle laterally stretches first combined-flow and the y-axle vertically stretches from the bed boundary on the thickness direction of the layer of first combined-flow along the lateral dimension of bed boundary:

(1) first combined-flow that comprises the layer that the coextrusion polymeric material separates is in the axial expansion of x-, and the interface between its middle level is in the x-z plane;

(2) first combined-flows are divided into many affluent-dividings along the x-axle;

(3) when along the z-axial flow when moving, affluent-dividing is redirected, and makes them stacked along the y-axle;

(4) affluent-dividing is again in conjunction with forming second combined-flow; With

(5) second combined-flows shrink along the y axle.

Layer multiplying assembly is positioned at after different polymer merged in the coextrusion assembly.After melt left layer multiplier, it was by die head and be manufactured with the film of the degree of crystallinity of hope.This method can use many extruders that first combined-flow is provided as required.First combined-flow can also use more than one series connection or the layer multiplier that is arranged in parallel and carry out layer multiplication.

Other manufacturing process are for example laminated, coating or extrude coating and can be used to make plural layers.For example, in laminated, under temperature and/or pressure, (for example use hot laminating roller or hot press) at the preformed layer that has necessary difference aspect the optical property and compile many, so that adjacent layer is bonded to each other.Film also can be made by the one or more layers of continuous curtain coating on one or more preformed layers.The layer or the material of anticipating the selection of plural layers for hope are not easy to the situation of coextrusion, extrude coating than above-mentioned melt coextrusion method more preferably.In extruding coating, on curtain coating fibre web, uniaxial orientation film or biaxially oriented film, extrude ground floor, then layer subsequently sequentially is coated on the layer that provides previously.The example of this method is a United States Patent (USP) 3741253.

In the manufacturing of plural layers, can adopt the combination of any above-mentioned technology.For example, can use more than two extruders and two or more coextruded films are laminated.

The layer of each type in the plural layers can be a uniaxial orientation, but preferably carries out biaxial orientation by stretching on two mutually perpendicular directions in thin film planar, to obtain satisfied comprehensive mechanical and physical property.Orientation can be carried out for example tubular or flat film technology by any method that is used for the production alignment films known in the art.

In tubular method, can pass through extrusioning thermoplastic plastic's polyester pipe, it is subsequently by quenching, heating and expanding causing horizontal orientation with air pressure inside then again, and causing machine-direction oriented speed to be pulled out, and carry out biaxial orientation simultaneously.

In preferred flat film method, cambial polymer by slot die extrude with on cooling curtain coating drum apace quenching to guarantee that polymer is become amorphous state by quenching.Then under the temperature of the glass transition temperature that is higher than polymer, the extrudate by stretching quenching at least one direction is orientated.Order orientation can by at first in a direction, usually vertically, promptly by the extrudate of the flat quenching that stretches on the direction of advance of film stretching machine, stretch in the horizontal then and carry out.The stretching easily forward on the roller of one group of rotation or carry out between two pairs of mip rolls of extrudate, cross directional stretch then carries out on the stenter device.Stretching proceeds to the degree by the decision of the character of polyester, for example PETG usually be stretched on the draw direction or on each draw direction alignment films be of a size of original size 2 to 5, more preferably 2.5 to 4.5 times.If only require orientation in one direction, can use bigger draw ratio (for example the highest about 8 times).If although wish to obtain the performance of balance, stretch comparably on vertical and horizontal, this is dispensable.

Oriented film can and preferably, by at the glass transition temperature that is being higher than polyester under the size restrictions condition but be lower than under the temperature of its melt temperature and carry out thermal finalization, cause crystallizing polyester and make dimensionally stable.Shrinkage at film is not in the of great concern application, and film can heat setting under lower temperature, does not perhaps carry out heat setting.On the other hand, the temperature of raising film heat setting can change the tear resistance of film.Therefore, actual heat-set temperature and time will change according to composition and its predetermined application of film, but the selection of these conditions should not make the tear-resistant performance of film worsen substantially.In these restrictions, about 135 to 235 ℃, preferably about 180 to 235 ℃ heat-set temperature are normally desirable.

Opaque plural layers of the present invention are highly-filled, preferably have at least 0.25, more preferably at least 0.5, especially at least 0.75 and ideally at least 1.0 transmitted light density (TOD).In one embodiment, TOD is 0.1 to 3.0, more preferably 0.25 to 2.5, more preferably 0.5 to 2.0 and especially 0.75 to 1.25.Give film with opacity by the blend polymer of the effective dose opacifying agent being introduced packed layer.The opacifying agent that is fit to comprises the mixture of inconsistent resin extender, particulate inorganic filler or two or more these class fillers, as describing hereinafter.

The whitness index that the surface of opaque film preferably has as what measure according to the description of this paper, is 60 to 120, more preferably 80 to 110, especially 90 to 105 and particularly 95 to 100 units.

When the outer surface of film be delustring the time obtained especially improved outward appearance attractive in appearance, the 60o gloss value that preferably has, as what measure, for being lower than 60%, more preferably 5% to 55%, especially 20% to 50% and particularly 35% to 45% according to description herein.

" inconsistent resin " is meant under the maximum temperature during the extruding and process of film neither also not miscible with the polymer basically resin of fusion.The existence of incompatible resin causes the layer of porous usually, and this is meant that this layer comprises microcellular structure, has the discrete closed pore of a certain at least ratio.The incompatible resin that is fit to comprises polyamide and olefin polymer, especially comprises the homopolymerization or the copolymer of the list-alpha-olefin of the highest 6 carbon atoms in the molecule.Preferable material comprises low or high density olefins homopolymers, especially polyethylene, polypropylene or poly 4-methylpene-1, olefin copolymer, especially ethylene-propylene copolymer, perhaps its two or more mixture.Can use random, block or graft copolymer.

Particulate inorganic filler comprises conventional inorganic filler, and especially metal or quasi-metal oxides, for example for example carbonate and the sulfate of calcium and barium of aluminium oxide, silica (particularly precipitated silica or diatomite and silica dioxide gel) and titanium dioxide, calcining magnetic soil and alkali metal salt.Particulate inorganic filler can be cavitation or non-cavitation type.The particulate inorganic filler that is fit to can be to be made up of single filler material or compound uniformly and basically, for example independent titanium dioxide or barium sulfate.Selectively, a certain proportion of at least filler can be heterogeneous, main filler material and additional modified component coupling.For example, main filler grain can be handled with surface modifier, and for example pigment, soap, surfactant coupling agent or other modifier are to improve or to change the filler degree compatible with polyester.

Preferred particulate inorganic filler comprises barium sulfate, titanium dioxide and silica, especially barium sulfate and titanium dioxide.

The barium sulfate particle can directly obtain from natural crystal (barite), perhaps obtain (plastic filler handbook (Hand book of Fillers for Plastics) by synthetic precipitation, H S Katz, J V Milewski.Van Nostrand Publishers, NewYork (1987)), for example be prepared by the precipitation reaction between barium salt and the metabisulfite solution.Synthetic BaSO ₄Usually than the higher purity that has derived from natural crystal, itself usually＞98.5%.Barium sulfate should be fine dispersion.Common available barite has the average diameter size of about 11 μ m, 6 μ m or 3 μ m.Synthetic BaSO ₄Average diameter less usually, be typically about 3 μ m, 1 μ m or 0.7 μ m.

TiO 2 particles can be anatase or rutile crystal form.TiO 2 particles preferably comprises the rutile of major part, more preferably the rutile of at least 60% weight, especially at least 80% weight and particularly about 100% weight.This particle can prepare by standardization program, for example chloride process or sulfate process.TiO 2 particles can apply, preferably with inorganic oxide for example aluminium, silicon, zinc, magnesium or its mixture.Preferred coatings also includes organic compounds, and for example aliphatic acid and preferably alkanol compatibly have 8 to 30, preferred 12 to 24 carbon atoms.Poly-diorganosiloxane or poly-organic group hydrogen siloxane, for example dimethyl silicone polymer or polymethyl hydrogen siloxane are the organic compounds that is fit to.This coating compatibly is applied to TiO 2 particles with aqueous suspension.For example sodium aluminate, aluminum sulfate, aluminium hydroxide, aluminum nitrate, silicic acid or sodium metasilicate precipitate inorganic oxide by water miscible compound in aqueous suspension.Coating on the TiO 2 particles is preferably the inorganic oxide of 1 to 12% weight and is preferably the organic compound of 0.5 to 3% weight, based on the weight of titanium dioxide.

Inorganic filler should be meticulous pulverizing, and the median particle diameter of its volume distributed median is (corresponding to the equivalent spherical diameter of 50% volume of all particles, it is read the integral distribution curve of particle diameter from volume %, be commonly referred to " D (v, 0.5) " value) be preferably 0.01 to 5 μ m, more preferably 0.05 to 5 μ m, more preferably 0.05 to 1.5 μ m, more preferably 0.15 to 1.2 μ m and especially 0.15 to 0.5 μ m.

Ideally, Zui Da particle should not have the size greater than packed layer thickness.Exist excessive particle can cause film to have inaesthetic ' spot ', promptly can with the naked eye find out to have single filler grain in the film.The particle that surpasses this size can be removed by method for sieving, and it is as known in the art.In preferred embodiments, particle size is controlled as the function of inorganic filler particle Size Distribution.Preferably, Size Distribution should make standard deviation be no more than 4 times D (v, 0.5) value, preferred 3 times D (v, 0.5) value and 2 times D (v, 0.5) value most preferably.As an illustration, D (the v of the mensuration of inorganic filler particle wherein, 0.5) value is 0.5 μ m, so at 99% particle at D (v, 0.5) value 3 times of standard deviation scopes in the basis on, preferred 9 9% filler grain is no more than 6.5 μ m, and (this numerical calculation is 0.5 μ m+3 * SD, SD=4 * 0.5 μ m wherein), preferred 99% filler grain is no more than 5.0 μ m (0.5 μ m+3 * SD, SD=3 * 0.5 μ m wherein), most preferably 99% filler grain is no more than 3.5 μ m (0.5 μ m+3 * SD, wherein SD=2 * 0.5 μ m).

The particle size of filler grain can pass through electron microscope, Coulter-counter, sedimentation analysis and static state or dynamic light scattering is measured.Technology based on laser diffraction is preferred.Median particle diameter can be by drawing the particle size that expression is lower than selection particle volume percentage integral distribution curve and measure 50% point and measure.

As required, the layer of polyester film can also comprise any other the additive that is generally used for making thin polymer film.Therefore, can add reagent for example dyestuff, pigment, cavitation reagent, lubricant, antioxidant, anti-blocking agent, surfactant, slip aids, glossiness improver, prodegradant, fire retardant, ultra-violet stabilizer, viscosity modifier and dispersion stabilizer according to circumstances.

In preferred embodiments, plural layers at least one the layer and preferably at least skin comprise one or more UV absorbents.The UV absorbent can be any well known by persons skilled in the art, and its raw material with other use that is used to prepare plural layers of the present invention is compatible.

In principle, can be with any organic or inorganic UV absorbent, especially be suitable for the sort of the present invention of being used for of polyester.The example that is fit to comprises and is disclosed in encyclopedia of chemical technology (Encyclopaedia of Chemical Technology), Kirk-Othmer, the third edition, John Wiley ﹠amp; Sons, the 23rd volume, the organic UV absorbent in the 615th to 627 page.The concrete example of UV absorbent comprises benzophenone, BTA (US-4684679, US-4812498 and US-4681905), benzoxazinone (US-4446262, US-5251064 and US-5264539) and triazine (US-3244708, US-3843371, US-4619956, US-5288778 and WO 94/05645).The instruction of above-mentioned document is hereby incorporated by.Preferably, this UV absorbent is nonvolatile and does not cause the excessive flavescence of product.

In one embodiment of the invention, the UV absorbent can chemically be introduced in the strand of cambial polyester.The preferred stable polyester of UV-is produced by benzophenone is introduced in the polyester, and for example described as EP-A-0006686, EP-A-0031202, EP-A-0031203 and EP-A-0076582, instruction wherein is hereby incorporated by.

In the preferred embodiment of the invention, the UV absorbent comprises one or more triazines, the more preferably hydroxyphenyltriazinuv compound of hydroxyphenyltriazinuv and especially general formula 1:

Wherein, R is hydrogen, C ₁-C ₁₈Alkyl, by halogen or C ₁-C ₁₂The C that alkoxyl replaces ₂-C ₆Alkyl, or benzyl and R ¹Be hydrogen or methyl.R is preferably C ₁-C ₁₂Alkyl or benzyl, more preferably C ₃-C ₆Alkyl and especially hexyl.R ¹Be preferably hydrogen.Particularly preferred UV absorbent is 2-(4,6-diphenyl-1,3,5-triazines-2-yl)-5-(hexyl) oxygen-phenol, and this compound can be from Ciba-Additives with Tinuvin ^TM1577 FF buy.Other example of preferred UV absorbent is that benzylidene malonate (can Sanduvor ^TMPR-25 buys from Sandoz) and benzoxazinone (can Cyasorb ^TM3638 buy from Cytec).

The inorganic UV absorbent that is fit to comprises metal oxide particle, for example zinc oxide or titanium dioxide.TiO 2 particles, for example previously described herein those, be especially preferred.

The amount of the UV absorbent in the introducing layer is generally 0.1% to 10%, more preferably 0.5% to 9%, more preferably 1.2% to 8%, especially 2% to 6% and particularly 3.2% to 5.5% weight with respect to the weight of the polymer of this layer.In one embodiment of the invention, have organic UV absorbent, preferred triazine and inorganic UV absorbent, preferred titanium dioxide both.The weight ratio of inorganic UV absorbent and organic UV absorbent is preferably 0.5 to 10: 1, more preferably 1 to 5: 1 and especially 1.5 to 2.5: 1.

The composition component of layer can conventional mode mix.For example, mixes, perhaps component and polymer are mixed by drum commentaries on classics blend or dried blend or by compounding in extruder, cool off then, and normally be crushed into particle or section with the monomer reactant of the polymer that forms this layer.Can also use female refining technology.

The existence of granular filler also improves film coiling during manufacture usually.Yet in order to improve coiling, film also can comprise " smooth coating ".The smooth coating that is fit to can be the discontinuity layer of acrylic compounds and/or methacrylic polymeric resin for example, and it randomly further comprises crosslinking agent, for example describes among the EP-A-0408197, and the disclosure is hereby incorporated by.Selectable smooth coating can comprise the potassium silicate coating, for example is disclosed in United States Patent (USP) 5925428 and 5882798, and the disclosure is hereby incorporated by.

Plural layers can also comprise printing ink-accept coating.Printing ink-accept coating to improve printing ink can easily be applied to this surperficial printing ink to the bonding of film and expansion scope.Printing ink-accept coating can be well-known any these type coatings of those skilled in the art.For example, printing ink-accept coating can comprise acrylic compounds component and linked (for example melamine formaldehyde (MF)), for example is disclosed in the coating among the EP-A-0429179, and the disclosure is hereby incorporated by.

According to another aspect of the present invention, the method that is used to make opaque tear-resistant film is provided, said method comprising the steps of: many polymer material layers are provided, wherein said many layers comprise the layer of the polymeric material of at least two fillings, the opacifying agent that wherein comprises at least 5% weight, at least two unfilled polyester material layers, laminated film wherein essentially no opacifying agent and that form described many layers.

According to another aspect of the present invention, provide two or more not filled polymer material layers that are substantially free of opacifying agent to be used to improve the purposes of the resistance to tearing of the opaque plural layers that comprise at least two filled polymer material layers, the layer of wherein said filling comprises the opacifying agent of at least 5% weight.

According to another aspect of the present invention, the method of the resistance to tearing of the opaque multilayer polymer film that is used to improve the polymer material layer that comprises at least two fillings is provided, the layer of wherein said filling comprises the opacifying agent of at least 5% weight, and described method comprises introduces described film with at least two unfilled polymer material layers that are substantially free of opacifying agent.

Opaque polymer film of the present invention has various uses, comprise usually purposes as the substitute (film that for example is used for drawing, demonstration, label, card (comprising identity card, smart card and credit card) and imaging) of paper, as the purposes of printed panel medium, purposes in packing and the purposes in coil coating.Described film also is favourable for the inwall that is laminated to metal can, especially tin can.Described film be particularly useful for need application than the opaque tear-resistant film of minimal thickness in, especially label and packaging applications.As mentioned above, thin thickness can be provided as this saving for the Price Sensitive meat market, and this is even more important in packaging applications.Described film also is particularly useful for requiring film product to have the application of high resistance to tearing.

Illustrate the present invention with reference to the following drawings, wherein:

Fig. 1 is the schematic diagram that is disclosed in the layer-multiplication equipment among the US-3051453 that is used to make plural layers.As shown in Figure 1,3-layer molten material flows is from the left side access to plant with at the right side separating device.The cross section of molten material flows is expressed as illustration (a) to (e).The position that in schematic representation of apparatus, has shown the dotted line A-A in the illustration (a).For illustration (b), (c) and (d), similarly section is shown as B-B, C-C and D-D respectively.So, illustration (a) to (e) has illustrated the drawing in side sectional elevation of sandwich construction, each stage coextrusion melt-flow during layer multiplication handled.With reference to illustration (a), as shown, three layers of compounding flux logistics carrying out layer-multiplication are in and enter before first multiplying assembly.Then this molten material flows respectively the stage (a) and (b) and (c) separated continuously, compression and compound.Illustrate the processing of repetition, it produces 9 layers of combined-flow, and it is transported to die head then.Further reprocessing comprises production the structure of 17 layers.

Fig. 2 is the schematic diagram of the layer-multiplication equipment that can be used for making plural layers.

With reference to figure 2, two-layer Composite Melt logistics (1) is by coextrusion module (2), then by four passage layers multipliers (3).Polymeric material provides 8 layers of combined-flow (5) by die head (4) then.

Fig. 3 B to 3D and Fig. 4 A to 4D graphic representation by analyzing the test data that the film produced as described in the following Examples obtains.Fig. 3 B below is provided the further discussion to 3D and 4A to 4D.

Following test method can be used for measuring some performance of film:

(i) the transmitted light density (TOD) of film uses BYKGardner Inc.Hazegard System to measure with transmission mode according to ASTM D1003-97.

(ii) the L* of the outer surface of white layer, a* and b* color coordinates value (CIE (1976)) and whitness index use Colorgard System2000, and model/45 (Pacific Scientific manufacturing) measured based on the principle of describing among the ASTM D313.

(iii) 60 of film surface ° of gloss values use Dr Lange reflectometer REFO 3 (deriving from Dr Bruno Lange, GmbH, Dusseldorf, Germany) to measure according to DIN67530.

(iv) film vertical and horizontal on both peak load and tear toughness, use Graves tear test (ASTM D1004-94A) and measure according to the description of this paper.

(v) stretch modulus and tensile elongation can be measured according to ASTM D882-88.

Further illustrate the present invention with reference to following examples.

Embodiment

Utilizing the standard flat film to extrude with the stenter method uses following material to make film:

Polymer " A ": gather (ethylene glycol terephthalate) (PET), its inherent viscosity (IV) is 0.63+/-0.02

Polymer " B ": PET, it comprises 20w/w% barium sulfate filler, and its IV is 0.63+/-0.02

Blend 1:100% polymer B

Blend 2:80% polymer B; 20% polymer A

Blend 3:70% polymer B; 30% polymer A

Blend 4:60% polymer B; 40% polymer A

Blend 5:50% polymer B; 50% polymer A

Polymer A and B are used to produce the not packed layer and the packed layer of plural layers respectively.Blend 1 to 5 is used to produce and is used for the single thin film that compares with plural layers.

Used fusion coextrusion system, wherein two independently extruder the polymer of molten condition is provided to common melt canal by the coextrusion injection module.The feature of this injection block is described two kinds of polymer molten fluids to be introduced common melt pipe, and keep the layer of separation in this common melt pipe.

The coextrusion melt be by cutting apart the system with compound fluid, makes that the number at the layer of the separation of melt canal interpolymer melt obtains increasing.This method of producing many polymeric layers from the initial flow of being made up of 3 layers is similar to the technology of describing the US-3051453 discussed above.If for comparative example's purpose is provided, identical polymer is fed in the melt system by each extruder, then can processes the polymer of one deck or individual layer.

Subsequently, molten polymer is extruded by the flat film die head, and as the melt films curtain coating to the chill roll of cold, rotation.After this, cast film experiences several further process segments.With the film charging by draw stage, wherein material under 90 ℃ in direction of advance or vertically be endowed 2.9 to 3.1 draw ratio.Apply ratio then and be 3.2 cross directional stretch, it carries out under 110 ℃ temperature by the tentering method, at last with the crystallization under about 220 ℃ temperature in the heat setting stage of twin shaft-alignment films.

Table 1 has shown the performance of the film of the process conditions of thin film fabrication and production.In order to estimate the characteristic of plural layers of the present invention, also prepared the single thin film of a series of respective thickness, so that compare.The data of optical density and peak load have been standardized as 80 μ m films.

Optical density that is shown in Table 1 and resistance to tearing data also be presented at Fig. 3 B to 3D and Fig. 4 A in 4D., in 3D, the function of optical density as packing density charted at Fig. 3 B.At Fig. 4 A in 4D, with tear-toughness is as the drawing of the function of packing density.

Fig. 4 A shows the data of tearing toughness data and individual layer comparative example 5 to 7 of comparative example 1 to 4 plural layers.

Fig. 3 B and 4B show embodiment 1 to 5 (9 layers) and individual layer comparative example's 8 to 11 opacity and tear toughness.

Fig. 3 C and 4C show embodiment 6 to 9 (17 layers) and individual layer comparative example's 12 to 14 opacity and tear the toughness data.

Fig. 3 D and 4D show embodiment 10 to 13 (17 layers) and individual layer comparative example's 15 to 17 opacity and tear the toughness data.

Fig. 3 B shows that to 3D for given filler loading, plural layers of the present invention with respect to the single thin film with corresponding loading filler, have the optical density of raising.

Fig. 4 B shows to 4D, is used for the filler of given loading, and plural layers of the present invention with respect to the single thin film with corresponding loading filler, unexpectedly have the bigger toughness of tearing.Fig. 4 A shows that three-layer thin-film does not demonstrate this effect, and its performance is similar with single thin film.

By this data of further analysis can clearer and more definite film of the present invention other advantages.

Can be clear that from Fig. 3 B for the opacity of the single thin film that reaches high filler loading capacity, plural layers must have about 1.02 optical density.The filling adding amount that obtaining this optical density in single thin film needs is about 19%, and for plural layers of the present invention, and this optical density can only use about 16% filler to obtain.

Therefore, for given optical density, plural layers of the present invention are more more economical than the production of the single thin film of prior art.

In addition, when contrast have suitable opacity these two kinds of films tear toughness the time, plural layers (about 16% filler) have about 0.42kg/mm ²Tear toughness, this almost is two times of single thin film (about 19% filler) with suitable opacity, the toughness of tearing of this single thin film is 0.26kg/mm ²

Table 1

Film	The number of plies	Membrane structure and composition	Feed rate *		Draw ratio (FD * SD)	Film thickness (μ m)	Total filler (%)	Optical density (standardization)	Graves tears experiment
			Feed rate *						Graves tears experiment				Logistics 1 Kg/hr	Logistics 2 kg/hr	Peak load (kgf)		Tear-toughness (kg/mm ²)
			??MD	???TD					??MD	??TD					Peak load (kgf)		Tear-toughness (kg/mm ²)
			??MD	???TD					??MD	??TD	Comparative Examples 1 Comparative Examples 2 Comparative Examples 3 Comparative Examples 4 Comparative Examples 5 Comparative Examples 6 Comparative Examples 7 embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 Comparative Examples 8 Comparative Examples 9 Comparative Examples 10 Comparative Examples 11 embodiment 6 embodiment 7 embodiment 8 embodiment 9 Comparative Examples 12 Comparative Examples 13 Comparative Examples 14 embodiment 10 embodiment 11 embodiment 12 embodiment 13 Comparative Examples 15 Comparative Examples 16 Comparative Examples 17	??3 ?? ??3 ??3 ??3 ??1 ??1 ??1 ??9 ??9 ??9 ??9 ??9 ??1 ??1 ??1 ??1 ??17 ??17 ??17 ??17 ??1 ??1 ??1 ??17 ??17 ??17 ??17 ??1 ??1 ??1			BAB BAB BAB BAB is single; Blend 5 is single; Blend 2 is single; Blend 1 (BA) ₄B ??(BA) ₄B ??(BA) ₄B ??(BA) ₄B ??(BA) ₄B is single; Blend 5 is single; Blend 4 is single; Blend 2 is single; Blend 1 (BA) ₈B ??(BA) ₈B ??(BA) ₈B ??(BA) ₈B is single; Blend 5 is single; Blend 3 is single; Blend 1 (BA) ₈B ??(BA) ₈B ??(BA) ₈B ??(BA) ₈B is single; Blend 5 is single; Blend 3 is single; Blend 1	??93 ? ??72 ??60 ??50 ??72 ??72 ??72 ??149 ??93 ??71 ??59 ??50 ??72 ??72 ??72 ??72 ??109 ??90 ??80 ??70 ??72 ??72 ??72 ??109 ??90 ??80 ??70 ??72 ??72 ??72	??40 ? ??48 ??60 ??75 ??48 ??48 ??48 ??40 ??40 ??48 ??60 ??75 ??48 ??48 ??48 ??48 ??50 ??56 ??60 ??65 ??48 ??48 ??48 ??50 ??56 ??60 ??65 ??48 ??48 ??48	??2.9×3.2 ?? ??2.9×3.2 ??2.9×3.2 ??2.9×3.2 ??2.9×3.2 ??2.9×3.2 ??2.9×3.2 ??3.1×3.2 ??3.1×3.2 ??3.1×3.2 ??3.1×3.2 ??3.1×3.2 ??3.1×3.2 ??3.1×3.2 ??3.1×3.2 ??3.1×3.2 ??3.1×3.2 ??3.1×3.2 ??3.1×3.2 ??3.1×3.2 ??3.1×3.2 ??3.1×3.2 ??3.1×3.2 ??2.9×3.2 ??2.9×3.2 ??2.9×3.2 ??2.9×3.2 ??2.9×3.2 ??2.9×3.2 ??2.9×3.2	??81 ? ??76 ??86 ??92 ??61 ??90 ??76 ??79.9 ??75.7 ??78.8 ??85.5 ??75.1 ??76.9 ??75.4 ??81.1 ??81.1 ??95.33 ??81.3 ??100.8 ??83.7 ??79.7 ??87.8 ??81.3 ??93.2 ??83.7 ??107.1 ??87.8 ??81.9 ??86.5 ??76.2	??12.9 ? ??11.3 ??9.6 ??7.9 ??10.5 ??16.2 ??19.6 ??16.1 ??15.7 ??13.1 ??11.1 ??8.6 ??9.4 ??11.1 ??14.7 ??18.7 ??19.3 ??17.9 ??17.2 ??11.6 ??10.9 ??15.4 ??21.4 ??19.3 ??17.9 ??17.2 ??11.6 ??10.9 ??15.4 ??21.4	??- ? ??- ??- ??- ??- ??- ??- ??1.05 ??0.95 ??0.85 ??0.76 ??0.75 ??0.55 ??0.65 ??0.71 ??1.02 ??0.99 ??1.07 ??0.88 ??0.86 ??0.62 ??0.86 ??1.13 ??0.90 ??0.96 ??0.77 ??0.77 ??0.49 ??0.74 ??1.07	??3.52 ? ??3.78 ??3.85 ??3.99 ??3.94 ??3.76 ??3.11 ??---- ??3.602 ??4.019 ??3.873 ??3.937 ??3.661 ??3.522 ??3.399 ??3.264 ??3.022 ??3.354 ??2.935 ??3.329 ??3.537 ??3.248 ??2.872 ??3.588 ??3.558 ??3.838 ??3.688 ??4.053 ??3.794 ??3.521	???- ? ???- ???- ???- ???- ???- ???- ???- ???- ???- ???- ???- ???- ???- ???- ???- ???2.769 ???3.091 ???2.743 ???3.122 ???3.459 ???2.837 ???2.517 ???3.285 ???3.294 ???3.273 ???3.366 ???3.535 ???3.413 ???3.205	??0.466 ? ??0.497 ??0.611 ??0.657 ??0.542 ??0.411 ??0.24 ??---- ??0.418 ??0.615 ??0.687 ??0.937 ??0.536 ??0.494 ??0.382 ??0.262 ??0.257 ??0.294 ??0.353 ??0.508 ??0.344 ??0.244 ??0.177 ??0.311 ??0.327 ??0.435 ??0.662 ??0.538 ??0.36 ??0.237	??- ? ??- ??- ??- ??- ??- ??- ??- ??- ??- ??- ??- ??- ??- ??- ??- ??0.291 ??0.321 ??0.35 ??0.401 ??0.377 ??0.25 ??0.179 ??0.329 ??0.339 ??0.402 ??0.57 ??0.419 ??0.296 ??0.208

* transferring polymer A and B are distinguished in logistics 1 and 2, and when the preparation single thin film, identical polymer is carried in logistics 1 and 2.

Claims

1. opaque plural layers, it comprises that at least two are substantially free of the unfilled polyester layer of opacifying agent and the polymer material layer of at least two fillings, the layer of wherein said filling comprises the opacifying agent of at least 5% weight.

2. the film of claim 1, the polymeric material of the layer of wherein said filling is a polyester.

3. the film of claim 1, wherein be substantially free of opacifying agent layer polymeric material and the opacifying agent that comprises at least 5% weight layer polymeric material identical.

4. any one film of aforementioned claim, the polymeric material in its middle level is poly-(ethylene glycol terephthalate).

5. any one film of aforementioned claim, wherein said opacifying agent is an inorganic particles packing.

6. any one film of aforementioned claim, wherein said opacifying agent is a barium sulfate.

7. any one film of aforementioned claim, the polymeric material that the layer of wherein said filling comprises the layer that accounts for this filling is the opacifying agent of 10 to 30% weight.

8. any one film of aforementioned claim, it comprises packed layer alternately and packed layer not.

9. any one film of aforementioned claim, it has sandwich construction (BA) _nB, wherein A represents unfilled layer, B represents that the layer and the n that fill are at least 2.

10. the film of claim 8, wherein n is at least 3.

11. any one film of aforementioned claim, the sum in its middle level be 7 or more than.

12. any one film of aforementioned claim, it has 0.3kg/mm at least at least one size of film ²Tear toughness, the described toughness of tearing is measured the area below the curve in the figure of strain with stress according to ASTM D1004-94A.

13. any one film of aforementioned claim, its transmitted light density is at least 0.5.

14. be used to make the method for opaque tear-resistant film, said method comprising the steps of: many polymer material layers are provided, wherein said many layers comprise the layer of the polymeric material of at least two fillings, the opacifying agent that wherein comprises at least 5% weight, at least two unfilled polyester material layers, wherein be substantially free of opacifying agent and form the laminated film of described many layers.

15. multi-layer film structure is used for providing at opaque polymer film the purposes of the resistance to tearing of raising, described multi-layer film structure comprises the layer of at least two unfilled polymeric materials, it is substantially free of opacifying agent, the layer of the polymeric material of at least two fillings, the layer of wherein said filling comprises the opacifying agent of at least 5% weight.

16. be used to improve the method for the resistance to tearing of opaque multilayer polymer film, this opaque multilayer polymer film comprises the layer of the polymeric material of at least two fillings, the layer of wherein said filling comprises the opacifying agent of at least 5% weight, described method is included in the layer of introducing at least two unfilled polymeric materials in the film, and the layer of this unfilled polymeric material is substantially free of opacifying agent.

17. two or more unfilled polymer material layers that are substantially free of opacifying agent are used to improve the purposes of the resistance to tearing of opaque plural layers, described plural layers comprise the polymer material layer of at least two fillings, and the layer of wherein said filling comprises the opacifying agent of at least 5% weight.

18. any one purposes, technology or method of claim 14 to 17, wherein said plural layers are that any one is defined as claim 1 to 13.